Boride-zirconium oxide-nitrogen carbide-based ceramics

ABSTRACT

Metallic boride-based ceramics having mechanical properties suited for use in extensive applications as abrasion-resistant and cutting tools are prepared by sintering a mixture essentially consisting of 20 to 88% by weight of one or more metallic borides and 10 to 70% by weight of a powder of zirconium oxide, with 2 to 70% by weight of one or more cubic nitrogen carbides selected from the group of Ti(C, N) and Zr(C, N).

FIELD OF THE INVENTION

This invention relates to a new type of metallic-boride-based sintered ceramics of high density suited for use as abrasion-resistant and cutting tool materials, and more particularly to boride-zirconium oxide-nitrogen carbide-based sintered ceramics.

BACKGROUND OF THE INVENTION

The inventors have proposed ceramics prepared by sintering a matrix of titanium diboride with the addition of zirconium dioxide (ZrO₂) (Japanese Patent Publication No. 7668 of 1984) and sintered ceramics prepared with the addition of cubic carbide (Japanese Patent Publication No. 7669 of 1984). These ceramics are suited for use as abrasion-resistant materials that are required to have considerable toughness. With the marked progress of industry in recent years, there are increasing demands for ceramics that are easier to sinter and have more improved properties.

Therefore, the inventors are continuing studies on the further improvement of the properties of metallic boride-zirconium oxide-metallic carbide-based ceramics.

When zirconium dioxide is added for the improvement of toughness, in particular, the zirconium dioxide stabilizer used together causes thermal deterioration. As such, composite ceramics sintered with zirconium dioxide stabilized by yttrium oxide (Y₂ O₃) or other similar stabilizer have been used only for services involving not much higher temperatures than the room temperature.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Through the studies to improve the sinterability and mechanical properties of metallic boride-zirconium oxide-carbide-based ceramics, the inventors discovered that the use of nitrogen carbide, which is a compound of metallic carbide and a solid solution of nitrogen, in place of metallic carbide permits lowering the sintering temperature while increasing deflective strength and toughness. It was also discovered that the use of monoclinic zirconium as zirconium oxide permits further improvement of thermal properties. These discoveries have resulted in this invention.

Generally, powders of borides tend to contain oxygen, and those containing oxygen are difficult to compact. Metallic carbide has a function to form a solid solution of the oxygen and removes it from the powders of borides. Metallic nitrogen carbide too was considered to have a similar property and high abrasion resistance against steel. After repeating sintering tests based on the above assumption, it was confirmed that metallic nitrogen carbide produces satisfactory results under certain conditions.

An object of this invention, which is based on the above knowledge, is to provide metallic boride-based ceramics having such mechanical properties as are suited for extensive applications as abrasion-resistant and cutting tools.

Another object of this invention is to provide metallic boride-based ceramics having such mechanical properties as are suited for extensive applications as abrasion-resistant and cutting tools that are heated to 200° C. or above.

This invention relates to metallic boride-based ceramics essentially consisting of a mixed powder of (A) 20 to 88% by weight, of the total weight of the mixture, of one or more of metallic borides expressed as MB₂ and M₂ B₅ (M denotes metal), (B) 10 to 70% by weight of zirconium dioxide (ZrO₂), and (C) 2 to 70% by weight of one or more of Ti(C, N) and Zr(C,N).

The main constituent (A) is a metallic boride selected from a group of such diborides as TiB₂, ZrB₂, CrB₂, VB₂, TaB₂, NbB₂, MnB₂, MoB₂, HfB₂, YB₂, AlB₂ and MgB₂ and such borides as W₂ B₅ and Mo₂ B₅ in which five atoms of metal combine with two atoms of boron. These borides may be used either singly or in combination.

The constituent (B) may be one or two of zirconium dioxides selected from a group of partially stabilized ZrO₂, tetragonal ZrO₂, cubic ZrO₂ and monoclinic ZrO₂. Addition of ZrO₂ should preferably be kept within the range of 10 to 70% by weight. In particular, addition of monoclinic ZrO₂, preferably within the range of 10 to 50% by weight, remarkably improves thermal properties with no deterioration resulting when heated at 250° C. for 200 hours. Adequate mechanical strength is not obtained outside the above range.

The cubic nitrogen carbide added as a third constituent is one or both of Ti(C, N) and Zr(C, N). This nitrogen carbide must constitute 2 to 70% by weight of the mixture. Outside this range, sintering and the improvement of the mechanical properties of the obtained sinter become difficult. When monoclinic ZrO₂ is used, Ti(C, N) should be preferably used as cubic nitrogen carbide.

Nitrogen carbide provides higher abrasion-resistance against steel than carbide, as mentioned previously. With some nitrogen removed during sintering, the solid solution of oxygen is formed with greater ease, which permits further improvement of properties.

When partially stabilized, tetragonal, cubic or monoclinic ZrO₂ is used, a compact sinter is obtained by forming an agglomerated mixture of the materials with a metal mold or rubber press and heating the formed product in a vacuum or in an atmosphere of inert, reducing, nitrogen or other gas at a temperature of 1400° to 1900° C. for 60 to 200 minutes. When monoclinic ZrO₂ is used, heating at 1400° to 1700° C. for 30 to 120 minutes is sufficient. The sinter may further be processed by hot isostatic pressing (HIP) or hot-pressing may be applied instead of vacuum sintering.

The metallic boride-based ceramics thus obtained are suited as materials for abrasion-resistant and cutting tools.

EXAMPLE 1

TiB₂ and Ti(C, N) classified to a particle size of not larger than 4 μm and partially stabilized ZrO₂ having a particle size of 0.02 μm were mixed in the ratio of 30:30:40 by weight. The mixture was agglomerated and formed with a rubber press under a pressure of 3 tons/cm² and then vacuum-sintered at 1700° C. for 90 minutes. The obtained sinter proved to have a deflective strength of 90 kg/mm², a Vickers hardness of Hv 1500, and a K_(I) C value of 6 MPam^(1/2) determined by the indentation method. Observation of the texture revealed no voids. This example is shown at No. 1 in Table 1. The specimens sintered by the same method and their properties are shown at Nos. 1 to 4 and 6 to 8.

EXAMPLE 2

TiB₂ and Ti(C, N) classified to a particle size of not larger than 4 μm and partially stabilized ZrO₂ having a particle size of 0.02 μm were mixed in the ratio of 30:30:40 by weight. The mixture was filled in a graphite mold and hot-pressed in a vacuum with a die pressure of 200 kg/cm² at 1700° C. for 60 minutes. The obtained sinter proved to have a deflective strength of 90 kg/mm², a Vickers hardness of Hv 1700, and a K_(I) C value of 4 MPam^(1/2) determined by the indentation method. Observation of the texture revealed no voids. This example is shown at No. 5 in Table 1. The specimens tested by the same method are shown at Nos. 9 and 10. The ZrO₂ used in the test was partially stabilized. Nos. 11 to 13 show the specimens tested for comparison. Generally, hot-pressed sinters are more compact, stronger and harder than vacuum-sintered products.

EXAMPLE 3

TiB₂ and Ti(C, N) classified to a particle size of not larger than 4 μm and monoclinic ZrO₂ were mixed in the ratio of 30:30:40 by weight. The mixed powder was hot-pressed in a vacuum at 1600° C. for 60 minutes. The obtained sinter proved to have a deflective strength of 700 MPa, a Vickers hardness of Hv 1650, and K_(I) C value of 7.5 MPam^(1/2) determined by the indentation method. The specimen developed no crack when heated at 250° C. for 300 hours in the atmosphere.

Table 2 shows other specimens prepared with the addition of monoclinic ZrO₂. The specimens with an asterisk were tested for the purpose of comparison.

                                      TABLE 1                                      __________________________________________________________________________     Spec-                                                                              Chemical                 Sintering Conditions                              imen                                                                               Composition              Sintering Temperature                                                                     Sintering Time                                                                         Atmos-                         No. (% by weight)            (°C.)                                                                              (Min.)  phere                          __________________________________________________________________________     1.  30% TiB.sub.2 --40% ZrO.sub.2 --30% Ti(C, N)                                                            1700       90      Vacuum                         2.  30% TiB.sub.2 --40% ZrO.sub.2 --30% Ti(C, N)                                                            1800       90      Vacuum                         3.  30% TiB.sub.2 --10% ZrO.sub.2 --60% Ti(C, N)                                                            1800       90      Vacuum                         4.  15% TiB.sub.2 --10% ZrO.sub.2 --75% Ti(C, N)                                                            1800       90      Vacuum                         5.  30% TiB.sub.2 --40% ZrO.sub.2 --30% Ti(C, N)                                                            1700       60      Vacuum                         6.  29% TiB.sub.2 --70% ZrO.sub.2 --1% Ti(C, N)                                                             1800       90      Vacuum                         7.  28.5% TiB.sub.2 --1.5% TaB.sub.2 --40% ZrO.sub.2 --30% Ti(C,                                            1600       90      Vacuum                         8.  5% TiB.sub.2 --20% ZrB.sub.2 --40% ZrO.sub.2 --35% Ti(C,                                                1600       90      Vacuum                         9.  20% ZrB.sub.2 --50% ZrO.sub.2 --30% Zr(C, N)                                                            1700       60      Vacuum                         10. 20% CrB.sub.2 --50% ZrO.sub.2 --30% Ti(C, N)                                                            1700       60      Vacuum                         11. TiB.sub.2 --40% ZrO.sub. 2                                                                              1800       60      Vacuum                         12. TiB.sub.2 --40% ZrO.sub.2 --30% TiC                                                                     1800       60      Vacuum                         13. 27% TiB.sub.2 --70% ZrO.sub.2 --3% Ti(C, N)                                                             1600       60      Vacuum                         __________________________________________________________________________                                  Properties of Sinter                              Spec-                                                                              Chemical                 Deflective                                                                           Hardness                                    imen                                                                               Composition              strength                                                                             at room                                                                               K.sub. IC                                                                          Void in                          No. (% by weight)            (Kg/mm.sup.2)                                                                        temperature                                                                           MPam.sup.1/2                                                                       texture                                                                            Remarks                      __________________________________________________________________________     1.  30% TiB.sub.2 --40% ZrO.sub.2 --30% Ti(C, N)                                                            90    1500   6   None                                                                               Vacuum                                                                         sintering                    2.  30% TiB.sub.2 --40% ZrO.sub.2 --30% Ti(C, N)                                                            90    1800   5   None                                                                               Vacuum                                                                         sintering                    3.  30% TiB.sub.2 --10% ZrO.sub.2 --60% Ti(C, N)                                                            60    1900   4   None                                                                               Vacuum                                                                         sintering                    4.  15% TiB.sub.2 --10% ZrO.sub.2 --75% Ti(C, N)                                                            60    1900   4   None                                                                               Vacuum                                                                         sintering                    5.  30% TiB.sub.2 --40% ZrO.sub.2 --30% Ti(C, N)                                                            90    1700   4   None                                                                               Hot                                                                            pressing                     6.  29% TiB.sub.2 --70% ZrO.sub.2 --1% Ti(C, N)                                                             20     900   8   None                                                                               Vacuum                                                                         sintering                    7.  28.5% TiB.sub.2 --1.5% TaB.sub.2 --40% ZrO.sub.2 --30% Ti(C,                                            100   1700   6   None                                                                               Vacuum                                                                         sintering                    8.  5% TiB.sub.2 --20% ZrB.sub.2 --40% ZrO.sub.2 --35% Ti(C,                                                100   1700   6   None                                                                               Vacuum                                                                         sintering                    9.  20% ZrB.sub.2 --50% ZrO.sub.2 --30% Zr(C, N)                                                            90    1700   6   None                                                                               Hot                                                                            pressing                     10. 20% CrB.sub.2 --50% ZrO.sub.2 --30% Ti(C, N)                                                            90    1700   6   None                                                                               Hot                                                                            pressing                     11. TiB.sub.2 --40% ZrO.sub.2                                                                               50    1500   4   None                                                                               Hot                                                                            pressing                     12. TiB.sub.2 --40% ZrO.sub.2 --30% TiC                                                                     70    1700   4   None                                                                               Hot                                                                            pressing                     13. 27% TiB.sub.2 --70% ZrO.sub.2 --3% Ti(C, N)                                                             80    1600   10  None                                                                               Hot                                                                            pressing                     __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________                                             Properties of Sinter                                           Sintering Conditions                                                                           De-  Hardness                          Spec-                                                                              Chemical           Sintering                                                                             Sintering flective                                                                            at room                           imen                                                                               Composition        Temperature                                                                           Time Atmos-                                                                              strength                                                                            tem- K.sub.                                                                             Void in                  No. (% by weight)      (°C.)                                                                          (Min.)                                                                              phere                                                                               (MPa)                                                                               perature                                                                            MPam.sup.1/2                                                                       texture                                                                            Remarks              __________________________________________________________________________     1.* 30% TiB.sub.2 --70% Ti(C, N)                                                                      1800   60   Vacuum                                                                              800  2100 3.5 None                                                                               Hot                                                                            pressing             2.  30% TiB.sub.2 --10% ZrO.sub.2 --60% Ti(C, N)                                                      1600   60   Vacuum                                                                              1200 1950 4.5 None                                                                               Hot                                                                            pressing             3.  30% TiB.sub.2 --20% ZrO.sub.2 --50% Ti(C, N)                                                      1600   60   Vacuum                                                                              800  1800 5.5 None                                                                               Hot                                                                            pressing             4.  30% TiB.sub.2 --30% ZrO.sub.2 --40% Ti(C, N)                                                      1600   60   Vacuum                                                                              800  1700 7.5 None                                                                               Hot                                                                            pressing             5.  30% TiB.sub.2 --40% ZrO.sub.2 --30% Ti(C, N)                                                      1600   60   Vacuum                                                                              700  1600 6.5 None                                                                               Hot                                                                            pressing             6.  30% TiB.sub.2 --50% ZrO.sub.2 --20% Ti(C, N)                                                      1600   60   Vacuum                                                                              700  1500 6.0 None                                                                               Hot                                                                            pressing             7.* 30% TiB.sub.2 --70% ZrO.sub.2                                                                     2000   60   Vacuum                                                                              400  --   --  Present                                                                            Hot                                                                            pressing             8.* 30% TiB.sub.2 --40% ZrO.sub.2 --30% TiC                                                           2000   60   Vacuum                                                                              700  1700 4.0 None                                                                               Hot                                                                            pressing             9.* 50% TiB.sub.2 --50% Ti(C, N)                                                                      1800   60   Vacuum                                                                              800  2200 3.5 None                                                                               Hot                                                                            pressing             10. 50% TiB.sub.2 --10% ZrO.sub.2 --40% Ti(C, N)                                                      1600   60   Vacuum                                                                              1000 2000 4.5 None                                                                               Hot                                                                            pressing             11. 50% TiB.sub.2 --20% ZrO.sub.2 --30% Ti(C, N)                                                      1600   60   Vacuum                                                                              800  1800 5.5 None                                                                               Hot                                                                            pressing             12. 50% TiB.sub.2 --30% ZrO.sub.2 --20% Ti(C, N)                                                      1600   60   Vacuum                                                                              800  1700 7.0 None                                                                               Hot                                                                            pressing             13. 50% TiB.sub.2 --40% ZrO.sub.2 --10% Ti(C, N)                                                      1600   60   Vacuum                                                                              850  1600 8.0 None                                                                               Hot                                                                            pressing             14.*                                                                               50% TiB.sub.2 --50% ZrO.sub.2                                                                     2000   60   Vacuum                                                                              500  --   --  None                                                                               Hot                                                                            pressing             15. 30% TiB.sub.2 --30% ZrO.sub.2 --40% Zr(C, N)                                                      1600   60   Vacuum                                                                              900  1700 7.0 None                                                                               Hot                                                                            pressing             16. 30% CrB.sub.2 --30% ZrO.sub.2 --40% Ti(C, N)                                                      1600   60   Vacuum                                                                              800  1700 7.0 None                                                                               Hot                                                                            pressing             17. 30% MoB--30% ZrO.sub.2 --40% Ti(C, N)                                                             1600   60   Vacuum                                                                              700  1700 7.0 None                                                                               Hot                                                                            pressing             18  30% FeB--30% ZrO.sub.2 --40% Ti(C, N)                                                             1600   60   Vacuum                                                                              800  1600 7.0 None                                                                               Hot                                                                            pressing             __________________________________________________________________________ 

What is claimed is:
 1. Boride-zirconium oxide-nitrogen carbide-based ceramics prepared by sintering a mixture consisting essentially of 20 to 88% by weight of one or more metallic borides and 10 to 70% by weight of a powder of zirconium oxide, with 2 to 70% by weight of one or more cubic nitrogen carbides selected from the group consisting of Ti(C, N) and Zr(C, N).
 2. Boride-zirconium oxide-nitrogen carbide-based ceramics according to claim 1, in which the powder of zirconium oxide consists of a powder of one or more zirconium oxides selected from the group consisting of tetragonal, cubic and monoclinic zirconium oxides.
 3. Boride-zirconium oxide-nitrogen carbide-based ceramics according to claim 1, in which the powder of zirconium oxide consists of a powder of monoclinic zirconium oxide.
 4. Boride-zirconium oxide-nitrogen carbide-based ceramics according to claim 3, in which 10 to 50% by weight of monoclinic zirconium oxide is mixed.
 5. Boride-zirconium oxide-nitrogen carbide-based ceramics according to claim 4, in which Ti(C, N) is used as the nitrogen carbide.
 6. Boride-zirconium oxide-nitrogen carbide-based ceramics according to any of claims 1 to 5, in which a compound consisting of one atom of metal combined with two atoms of boron or a compound consisting of five atoms of metal combined with two atoms of boron is used as the metallic boride. 